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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Prediction of prompt NO(x) in hydrocarbon air flames

The gas turbine industry is directing particular attention to very low NOx combustors, whether for aircraft or land based CCGT systems. These low NOx combustors frequently use liquid fuels or natural gas burning under very lean premixed conditions with air or under rich-lean conditions, although only the first case is studied here. In land based systems, diluted steam or nitrogen are sometimes injected into the combustion chambers to reduce flame temperature. The NOx emissions from such systems are the product of three chemical mechanisms which are interrelated: the hydrocarbon prompt NO, the thermal NO (extended Zeldovich mechanism), and the nitrous oxide route to NO. Formation of NO2 from NO also occurs, as well as emission of carbon monoxide and unburnt hydrocarbons. When the fuel-oxidant proportion decreases towards leaner conditions, flame temperatures are lowered, resulting in the total NO being reduced and the thermal-NO contribution greatly diminished to the benefit of the remaining two mechanisms of NO formation. While knowledge of the elementary reactions and their chemical kinetics concerning methane and simple hydrocarbons combustion has existed for a number of years, its use for computer modeling is limited to simple flow dynamics configurations. Nevertheless, understanding of such combusting flows under a wide range of experimental conditions allows for analogies or speculations with more complex actual systems. Such understanding can be achieved by means of one dimensional laminar premixed flame modeling, with a full chemical mechanism which incorporates the three routes of NO formation. Complementary to this understanding is the modeling of the actual combustion system using a full description of the fluid dynamics coupled with a reduced chemical scheme, which is then compared against the first model. The objective of this investigation is to evaluate the relative importance of the three mechanisms of NO formation in lean premixed methane-air combustion with increasing pressure using the one dimensional plug flow package PREMIX, and to test the validity of a three dimensional model with a global chemical mechanism against the one dimensional model in the atmospheric pressure case. Methane is chosen because it is the only mechanism which is reasonably well known and is a good guide to the behavior of other hydrocarbons. The mixture ratio chosen is richer than that in lean gas turbines, but the combustion of this mixture with the low preheat gives realistic gas turbine final flame temperatures. Conditions of NO2 formation are also analyzed in the one dimensional model and results extrapolated to the case of gas turbines.

Valerie Dupont↗
NASA NTRS1992

Study of basic physical processes in liquid rocket engines

Inconsistencies between analytical results and measurements for liquid rocket thrust chamber performance, which escape suitable explanations, have motivated the examination of the basic phys ical modeling formulations as to their unlimited application. The publication of Prof. D. Straub's book, 'Thermofluid-dynamics of Optimized Rocket Propulsions,' further stimulated the interest of understanding the gas dynamic relationships in chemically reacting mixtures. A review of other concepts proposed by Falk-Ruppel (Gibbsian Thermodynamics), Straub (Alternative Theory, AT), Prigogine (Non-Equilibrium Thermodynamics), Boltzmann (Kinetic Theory), and Truesdell (Rational Mechanism) has been made to obtain a better understanding of the Navier-Stokes equation, which is now used extensively for chemically reacting flow treatment in combustion chambers. In addition to the study of the different concepts, two workshops were conducted to clarify some of the issues. The first workshop centered on Falk-Ruppel's new 'dynamics' concept, while the second one concentrated on Straub's AT. In this report brief summaries of the reviewed philosophies are presented and compared with the classical Navier-Stokes formulation in a tabular arrangement. Also the highlights of both workshops are addressed.

Wu, S. T.↗
NASA NTRS1995

Dynamics and structure of turbulent premixed flames

In earlier work (Mantel & Bilger, 1994) the structure of the turbulent premixed flame was investigated using statistics based on conditional averaging with the reaction progress variable as the conditioning variable. The DNS data base of Trouve and Poinsot (1994) was used in this investigation. Attention was focused on the conditional dissipation and conditional axial velocity in the flame with a view to modeling these quantities for use in the conditional moment closure (CMC) approach to analysis of kinetics in premixed flames (Bilger, 1993). Two remarkable findings were made: there was almost no acceleration of the axial velocity in the flame front itself; and the conditional scalar dissipation remained as high, or higher, than that found in laminar premixed flames. The first finding was surprising since in laminar flames all the fluid acceleration occurs through the flame front, and this could be expected also for turbulent premixed flames at the flamelet limit. The finding gave hope of inventing a new approach to the dynamics of turbulent premixed flames through use of rapid distortion theory or an unsteady Bernoulli equation. This could lead to a new second order closure for turbulent premixed flames. The second finding was contrary to our measurements with laser diagnostics in lean hydrocarbon flames where it is found that conditional scalar dissipation drops dramatically below that for laminar flamelets when the turbulence intensity becomes high. Such behavior was not explainable with a one-step kinetic model, even at non-unity Lewis number. It could be due to depletion of H2 from the reaction zone by preferential diffusion. The capacity of the flame to generate radicals is critically dependent on the levels of H2 present (Bilger, et al., 1991). It seemed that a DNS computation with a multistep reduced mechanism would be worthwhile if a way could be found to make this feasible. Truly innovative approaches to complex problems often come only when there is the opportunity to work close at hand with the (in this case numerical) experimental data. Not only can one spot patterns and relationships in the data which could be important, but one can also get to know the limitations of the technique being used, so that when the next experiment is being designed it will address resolvable questions. A three-year grant from the Australian Research Council has enabled us to develop a small capability at the University of Sydney to work on DNS of turbulent reacting flow, and to analyze data bases generated at CTR. Collaboration between the University of Sydney and CTR is essential to this project and finding a workable modus operandum for this collaboration, given the constraints involved, has been a major objective of the past year's effort. The overall objectives of the project are: (1) to obtain a quantitative understanding of the dynamics of turbulent premixed flames at high turbulence levels with a view to developing improved second order closure models; and (2) to carry out new DNS experiments on turbulent premixed flames using a carefully chosen multistep reduced mechanism for the chemical kinetics, with a view to elucidating the laser diagnostic findings that are contrary to the findings for DNS using one-step kinetics. In this first year the objectives have been to make the existing CTR data base more accessible to coworkers at the University of Sydney, to make progress on understanding the dynamics of the flame in this existing CTR data base, and to carefully construct a suitable multistep reduced mechanism for use in a new set of DNS experiments on turbulent premixed flames.

Bilger, R. W.↗
NASA NTRS1993

Chemistry and transport in a multi-dimensional model

The focus of our research program is the achievement of a quantitative understanding of the spatial distribution and temporal variation of chemical species in the terrestrial middle atmosphere, with emphasis on ozone. Although not directed at assessments of anthropogenic impacts, our activities contribute to a refinement of model descriptions of chemical and dynamical processes that are needed for assessment tasks. A unique feature of our research effort is a close interaction with the chemical kinetics group at JPL and the field measurement groups at JPL. The principal tools used in our investigations are l-D and 2-D photochemical models. The advective component of the meridional transport in these models is approximated by the diabatic circulation, which is derived diagnostically from the net radiative heating rates. We are developing accurate radiative transfer algorithms to find the net heating rates and the diabatic circulation for use in the 2-D model.

Yung, Yuk L.↗
NASA NTRS2017

Predictive Modeling of Fast-Curing Thermosets in Nozzle-Based Extrusion

This work presents an approach to modeling the dynamic spreading and curing behavior of thermosets in nozzle-based extrusions. Thermosets cover a wide range of materials, some of which permit low-temperature processing with subsequent high-temperature and high-strength working properties. Extruding thermosets may overcome the limited working temperatures and strengths of conventional thermoplastic materials used in additive manufacturing. This project aims to produce technology for the fabrication of thermoset-based structures leveraging advances made in nozzle-based extrusion, such as fused deposition modeling (FDM), material jetting, and direct writing. Understanding the synergistic interactions between spreading and fast curing of extruded thermosetting materials will provide essential insights for applications that require accurate dimensional controls, such as additive manufacturing [1], [2] and centrifugal coating/forming [3]. Two types of thermally curing thermosets -- one being a soft silicone (Ecoflex 0050) and the other being a toughened epoxy (G/Flex) -- served as the test materials in this work to obtain models for cure kinetics and viscosity. The developed models align with extensive measurements made with differential scanning calorimetry (DSC) and rheology. DSC monitors the change in the heat of reaction, which reflects the rate and degree of cure at different crosslinking stages. Rheology measures the change in complex viscosity, shear moduli, yield stress, and other properties dictated by chemical composition. By combining DSC and rheological measurements, it is possible to establish a set of models profiling the cure kinetics and chemorheology without prior knowledge of chemical composition, which is usually necessary for sophisticated mechanistic modeling. In this work, we conducted both isothermal and dynamic measurements with both DSC and rheology. With the developed models, numerical simulations yielded predictions of diameter and height of droplets, along with width and height of extruded lines cured at varied temperatures. Experimental results carried out on a goniometric platform and a nozzle-based 3D printer showed agreement with the numerical simulations. Finally, this presentation will show how the models are adaptable to the planning of tool paths and designs in additive manufacturing.

Xie, Jingjin↗
NASA NTRS1978

Characterization of a swept-strut hydrogen fuel-injector for scramjet applications

Results of an experimental investigation of a swept-strut hydrogen fuel-injector simulating the center strut of a three strut scramjet module at Mach 6 flight conditions are presented. Detailed wall pressure distributions from over 100 separate tests with overall fuel flow from 0.1 to 1.3 times stoichiometric and test gas stagnation temperature from 1100 to 2400 K were recorded. The distance for pressure rise from the point of injection was found to increase with increasing test stagnation temperature. This trend indicates that chemical kinetics in the immediate region of perpendicular injection are not likely to be the mechanism controlling the onset of pressure rise. A fluid dynamic mechanism is suggested involving separation of the boundary layer downstream of injection which is forced upstream from the trailing edge by pressure rise due to combustion occurring in the base region of the strut. The results obtained indicate that the swept-strut fuel-injector concept can be adapted to a wide range of flight conditions by varying the amount of perpendicular fuel injection.

Northam, G. B.↗
NASA NTRS1997

Premixed Gas Combustion: An Excitable System

Rotating spiral and target patterns have been observed experimentally on freely-propagating premixed gas flames in large diameter tubes at normal gravity (1-g). These modes of propagation occur in near-limit mixtures which have a Lewis number (Le, defined as the ratio of the thermal diffusivity of the cold mixture to the mass diffusivity of the scarce component into the mixture) sufficiently greater than one. However, at 1-g, buoyant flows strongly distort the flame curvature, hydrodynamics (thus stretch) and convective transport of species and heat. In turn, these alter the critical Le required for onset of instability. To isolate and better understand the mechanisms which drive the observed patterns and their dynamics, 1-g and microgravity (micro-g) experiments are being conducted to determine: (1) the structure and dynamics of the patterns, (2) a map of the critical Le and heat loss for their occurrence, (3) the relative significance of the chemical kinetics, and (4) the effect of curvature (local wave and global flame front) on wave propagation. With this in hand, we will be better prepared to discuss an additional mode, a state of 'chemical turbulence,' which seems to be the ultimate fate of many of these near-limit flames prior to extinction.

Pearlman, Howard↗
NASA NTRS1985

Liquid rocket combustor computer code development

The Advanced Rocket Injector/Combustor Code (ARICC) that has been developed to model the complete chemical/fluid/thermal processes occurring inside rocket combustion chambers are highlighted. The code, derived from the CONCHAS-SPRAY code originally developed at Los Alamos National Laboratory incorporates powerful features such as the ability to model complex injector combustion chamber geometries, Lagrangian tracking of droplets, full chemical equilibrium and kinetic reactions for multiple species, a fractional volume of fluid (VOF) description of liquid jet injection in addition to the gaseous phase fluid dynamics, and turbulent mass, energy, and momentum transport. Atomization and droplet dynamic models from earlier generation codes are transplated into the present code. Currently, ARICC is specialized for liquid oxygen/hydrogen propellants, although other fuel/oxidizer pairs can be easily substituted.

Liang, P. Y.↗
NASA NTRS1999

Quantitative Species Measurements in Microgravity Combustion Flames using Near-Infrared Diode Lasers

Understanding the physical phenomena controlling the ignition and spread of flames in microgravity has importance for space safety as well as for characterizing dynamical and chemical combustion processes which are normally masked by buoyancy and other gravity-related effects. Unfortunately, combustion is highly complicated by fluid mechanical and chemical kinetic processes, requiring the use of numerical modeling to compare with carefully designed experiments. More sophisticated diagnostic methods are needed to provide the kind of quantitative data necessary to characterize the properties of microgravity combustion as well as provide accurate feedback to improve the predictive capabilities of the models. Diode lasers are a natural choice for use under the severe conditions of low gravity experiments. Reliable, simple solid state operation at low power satisfies the operational restrictions imposed by drop towers, aircraft and space-based studies. Modulation wavelength absorption spectroscopy (WMS) provides a means to make highly sensitive and quantitative measurements of local gas concentration and, in certain cases, temperature. With near-infrared diode lasers, detection of virtually all major combustion species with extremely rapid response time is possible in an inexpensive package. Advancements in near-infrared diode laser fabrication technology and concurrent development of optical fibers for these lasers led to their use in drop towers. Since near-infrared absorption line strengths for overtone and combination vibrational transitions are weaker than the mid-infrared fundamental bands, WMS techniques are applied to increase detection sensitivity and allow measurement of the major combustion gases. In the first microgravity species measurement, Silver et al. mounted a fiber-coupled laser at the top of the NASA 2.2-sec drop tower and piped the light through a single-mode fiber to the drop rig. A fiber splitter divided the light into eight channels that directed the laser beam across a methane or propane diffusion jet flame. The light beams were recaptured by a set of gradient index lenses, coupled back into separate fiber optic lines, and transmitted back to detectors and electronics in the instrument package. In these experiments a 6-mm od fiber cable (containing the nine optical fibers) fell with the drop rig. Using separate detection and demodulation channels, spatial and temporal (up to 20 Hz) maps of water vapor and methane concentrations were obtained at differing heights in the flames. While this apparatus was useful from a demonstration standpoint, several drawbacks needed attention before useful scientific measurements could be obtained. First, eight lines of sight are somewhat insufficient for detailing the spatial profiles of the gas. Second, multiple detection channels operating in parallel are both expensive and present a challenge for accurate calibration. As a result, a newer scanning system was developed in our first contract under this program. The primary characteristic of this system is that it contains a single detection channel and achieves "continuous" spatial resolution by scanning the laser beam across the flame region, then directing this beam onto a single detector. Thus spatial measurements are converted to a temporal series of data. The true spatial resolution is limited only by the beam diameter and width of the sweep. In these experiments the beam is focused to about 1-mm diameter and scans across a region up to 4-cm wide.

Silver, Joel A.↗
NASA NTRS1995

The effects of sooting in droplet combustion

The study of the burning of a single droplet is an ideal problem from which to gain fundamental understanding of diffusion flame characteristics. Droplet combustion is a complex physico-chemical process that involves a chemically-reacting two-phase flow with phase changes and yet simple experiments and analysis can be used to attain important insights into the burning rate, flame dynamics, kinetic extinction and disruption processes. It is a subject that has been actively studied for the past 40 years with most of the fundamental experiments being performed under reduced-gravity conditions for direct comparisons with theoretical/computational analyses that invoke spherical symmetry assumptions. In the earlier studies, the effects of sooting on the overall burning characteristics were not considered. However, recent microgravity investigations performed at the NASA-LeRC droptowers (Droplet Combustion Experiment) and others indicate that effects of soot and sootcloud formation may be significant during the lifetime of the droplet and therefore must be included in the analysis.

Lee, Kyeong-Ook↗
NASA NTRS1999

Low-Temperature Oxidation Reactions and Cool Flames at Earth and Reduced Gravity

Non-isothermal studies of cool flames and low temperature oxidation reactions in unstirred closed vessels are complicated by the perturbing effects of natural convection at earth gravity. Buoyant convection due to self-heating during the course of slow reaction produces spatio-temporal variations in the thermal and thus specie concentration fields due to the Arrhenius temperature dependence of the reaction rates. Such complexities have never been quantitatively modeled and were the primary impetus for the development of CSTR's (continuously stirred tank reactors) 30 years ago. While CSTR's have been widely adopted since they offer the advantage of spatial uniformity in temperature and concentration, all gradients are necessarily destroyed along with any structure that may otherwise develop. Microgravity offers a unique environment where buoyant convection can be effectively minimized and the need for stirring eliminated. Moreover, eliminating buoyancy and the need for stirring eliminates complications associated with the induced hydrodynamic field whose influence on heat transport and hot spot formation, hence explosion limits, is not fully realized. The objective of this research is to quantitatively determine and understand the fundamental mechanisms that control the onset and evolution of low temperature reactions and cool flames in both static and flow reactors. Microgravity experiments will be conducted to obtain benchmark data on the structure (spatio-temporal temperature, concentration, flow fields), the dynamics of the chemical fronts, and the ignition diagrams (pressure vs. temperature). Ground-based experiments will be conducted to ascertain the role of buoyancy. Numerical simulations including detailed kinetics will be conducted and compared to experiment.

Pearlman, Howard↗
NASA NTRS2002

Spray and High-Pressure Flow Computations in the National Combustion Code (NCC) Improved

Sprays occur in a wide variety of industrial and power applications and in materials processing. A liquid spray is a two-phase flow with a gas as the continuous phase and a liquid as the dispersed phase in the form of droplets or ligaments. The interactions between the two phases--which are coupled through exchanges of mass, momentum, and energy--can occur in different ways at disparate time and length scales involving various thermal, mass, and fluid dynamic factors. An understanding of the flow, combustion, and thermal properties of a rapidly vaporizing spray requires careful modeling of the ratecontrolling processes associated with turbulent transport, mixing, chemical kinetics, evaporation, and spreading rates of the spray, among many other factors. With the aim of developing an efficient solution procedure for use in multidimensional combustor modeling, researchers at the NASA Glenn Research Center have advanced the state-of-the-art in spray computations in several important ways.

Raju, Manthena S.↗
NASA NTRS2023

Chemical Thermodynamics and the Mathematical Integration of Reaction Kinetics

Key advances in the development of numerical methods for non-reacting compressible flows have been enabled by translating physical requirements into concrete numerical guidelines, such as the satisfaction of entropy inequalities for shock-capturing techniques [Lax, Contributions to Nonlinear Functional Analysis (1971) 603-634]. In the present work, we present nonlinear numerical analysis tools that draw from Chemical Thermodynamics , the branch of Nonequilibrium Thermodynamics that deals with chemical reactions. Through Gibbs formalism, chemical thermodynamics provides a well-known theoretical expression for the chemical equilibrium constant of a reaction in terms of reduced chemical potentials. A less-known, yet extremely valuable result, due to [Krambeck, Arch. Ration. Mech. Anal. , 38 (1970) 317], states that when this expression is implemented, mass-action kinetic models are consistent with the dynamical prescriptions of the 2nd law of thermodynamics. For fixed-temperature ordinary differential equations modeling constant-volume reacting gas mixtures, this leads to a decreasing Helmholtz free energy. If the temperature is allowed to vary in accordance with conservation of energy (1st law), this leads to the statement of increasing entropy. These nonlinear prescriptions can, and should be, used to further develop temporal integration techniques for reaction kinetics. We demonstrate that Krambeck's result holds even when the equilibrium constants are approximated from data. We prove this result by constructing the implicit free energy and the implicit entropy inherent to a given approximation. This is first done for a 5-species, 17-reaction model problem for air. With this structure established, elements of discrete entropy-stability theory [Tadmor, Acta Numer. , 12 (2003) 451] are leveraged to examine the consistency of time-integration schemes with these prescriptions. Using chemical potentials, one can compute the respective contributions of the kinetics model and of the temporal scheme to free energy/entropy variations. We introduce a nonlinear-stable version of the Discontinuous-Galerkin (DG) scheme in time which shows robustness improvements over the standard linearly-stable version. Most notably, the maximum timestep that can be resolved with the nonlinearly-stable variant tends to grow with polynomial order, in contrast to the linearly-stable variant. We generalize our constructions to arbitrary systems of reversible chemical reactions, ultimately showing that the compressible reacting Euler system admits the opposite of the implicitly constructed thermodynamic entropy as a mathematical entropy . This lays important theoretical foundations towards robust scheme development [Harten, J. Comput. Phys. 49 (1983) 151-164].

STMD↗
NASA NTRS2003

Dynamical Study of Prebiotic Processing by Comet Impact

Comets and meteoroids that bombarded the Earth, other planets and moons are considered possible deliverers of prebiotic materials manufactured in space. Simultaneously, chemical processing can be initiated by the large kinetic energy imparted to the planetary atmosphere during comet/meteoroid entry. The efficiency of organic synthesis and the diversity of products by impact shock are known to decrease as the reducing power of the atmosphere decreases. It is generally accepted that rich organic products are produced in a methane atmosphere whereas a carbon dioxide atmosphere is reported to yield a dearth of products In order to understand the details of impact chemistry and how it depends on the atmospheric composition, we carried out simulations of the chemistry initiated by comet/meteoroid impact upon a planetary atmosphere using different atmospheric compositions. The simulations were done by solving the set of coupled equations for mass, momentum, and energy conservations, chemical kinetics, and transport, that describe a high-energy impact shock, subsequent expansion and cooling of the hot shocked gas by mixing with the ambient gas, and the eventual steady state composition.

Huo, Winifred M.↗
NASA NTRS1972

The Aladdin experiment. I - Dynamics.

A coordinated rocket experiment was carried out on Nov. 20, 1970 at Eglin AFB, Fla. (30 deg N) to determine atmospheric layering and density distributions of ions and neutrals. The program measured vertical profiles between 70 and 150 km altitude of total neutrals, ions and electrons, individual species, temperature, density, diffusion coefficients, horizontal winds, and turbulent structure. A dynamic computer code model using these parameters was compared with the observed profiles. Wind fields were measured from seven chemical trails, separated up to 60 km horizontally and 600 sec in time. Kinetic temperatures were measured from fluorescence of chemically-released AlO, ranging from 440 to 680 K between 126 and 161 km. Densities derived from diffusion of the AlO ranged from 10 to 5 times 10 to the -12th power per cu cm between 126 and 139 km. A rocket-borne pitot probe showed wavelike density deviations from current standard atmosphere models, amounting to -25% at 80 and 110 km and to +25% at 100 and 125 km. The derived temperature profile from the pitot probe showed a double minimum at 74 and 102 km.

Rosenberg, N. W.↗
NASA NTRS1998

LSPRAY: Lagrangian Spray Solver for Applications With Parallel Computing and Unstructured Gas-Phase Flow Solvers

Sprays occur in a wide variety of industrial and power applications and in the processing of materials. A liquid spray is a phase flow with a gas as the continuous phase and a liquid as the dispersed phase (in the form of droplets or ligaments). Interactions between the two phases, which are coupled through exchanges of mass, momentum, and energy, can occur in different ways at different times and locations involving various thermal, mass, and fluid dynamic factors. An understanding of the flow, combustion, and thermal properties of a rapidly vaporizing spray requires careful modeling of the rate-controlling processes associated with the spray's turbulent transport, mixing, chemical kinetics, evaporation, and spreading rates, as well as other phenomena. In an attempt to advance the state-of-the-art in multidimensional numerical methods, we at the NASA Lewis Research Center extended our previous work on sprays to unstructured grids and parallel computing. LSPRAY, which was developed by M.S. Raju of Nyma, Inc., is designed to be massively parallel and could easily be coupled with any existing gas-phase flow and/or Monte Carlo probability density function (PDF) solver. The LSPRAY solver accommodates the use of an unstructured mesh with mixed triangular, quadrilateral, and/or tetrahedral elements in the gas-phase solvers. It is used specifically for fuel sprays within gas turbine combustors, but it has many other uses. The spray model used in LSPRAY provided favorable results when applied to stratified-charge rotary combustion (Wankel) engines and several other confined and unconfined spray flames. The source code will be available with the National Combustion Code (NCC) as a complete package.

Raju, Manthena S.↗
NASA NTRS1982

Mechanisms of droplet combustion

The fundamental physico-chemical mechanisms governing droplet vaporization and combustion are discussed. Specific topics include governing equations and simplifications, the classical d(2)-Law solution and its subsequent modification, finite-rate kinetics and the flame structure, droplet dynamics, near- and super-critical combustion, combustion of multicomponent fuel blends/emulsions/suspensions, and droplet interaction. Potential research topics are suggested.

Law, C. K.↗
NASA NTRS1998

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Shock, Everett L.↗